New Perspectives for Old Clusters: Anderson–Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d–4 f Species

A series of nine [Sb₇W₃₆O₁₃₃Ln₃M₂(OAc)(H₂O)₈]^17? heterometallic anions ( Ln₃M₂ ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW₉O₃₃} capping unit formed by a planar {MW₆O₂₄} fragment to which three {WO₂} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW₆O₂₄} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln₃M₂ anions possess chirality owing to a {Sb₄O₄} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce₃Co₂ derivative.     

Sol-gel synthesis of ZnO/Zn<Subscript>2-x</Subscript>Fe<Subscript>x</Subscript>TiO<Subscript>4</Subscript> powders: structural properties,electrical conductivity and dielectric behavior

The aim of this work was an investigation of structural and electrical properties of ZnO/Zn_2-xFe_xTiO₄ (x?=?0.7, 1, 1.4) powders. The compounds obtained by sol-gel method are characterized by several techniques: X-ray diffraction (XRD), N₂ adsorption–desorption isotherms, scanning and transmission electron microscopy (SEM and TEM), X-ray photoelectron spectroscopy (XPS), electrical and dielectrical measurements. The XRD, SEM and XPS analysis confirmed the formation of ZnFeTiO₄ inverse spinel structure. The electrical and dielectrical properties of ZnO/Zn_2-xFe_xTiO₄ (x?=?0.7, 1, 1.4) were measured by impedance spectroscopy, revealing a decrease in the electrical conductivity and the dielectric constant with Fe content.

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Controlling Dual Molecular Pumps Electrochemically

Artificial molecular machines can be operated using either physical or chemical inputs. Light‐powered motors display clean and autonomous operations, whereas chemically driven machines generate waste products and are intermittent in their motions. Herein, we show that controlled changes in applied electrochemical potentials can drive the operation of artificial molecular pumps in a semi‐autonomous manner—that is, without the need for consecutive additions of chemical fuel(s). The electroanalytical approach described in this Communication promotes the assembly of cyclobis(paraquat‐p‐phenylene) rings along a positively charged oligomeric chain, providing easy access to the formation of multiple mechanical bonds by means of a controlled supply of electricity.     

Characterization of the complexing agents’ influence on bioscouring cotton fabrics by FT-IR and TG/DTG/DTA analysis

The nature of the complexing agents used in the bioscouring process of cotton fabrics aiming to eliminate the non-cellulosic compounds (pectin, waxes, etc.) and to improve the hydrophilic and wetting properties influences the thermal behaviour and the FT-IR spectra of the textile materials. In this paper, we study the influence of the experimental conditions and complexing agent nature (sodium citrate or disodium EDTA salt) on the pectin elimination in bioscouring treatment of cotton fabric by FT-IR and TG/DTG/DTA analysis. The changes from FT-IR spectra of the specific bands (absorbance intensity at 2916, 2852, 1732 and 1640/1642 cm^?1) were evaluated. The thermal behaviour of the investigated samples’ fabric by using TG/DTG/DTA analysis was studied at 30–600 °C temperature range, in air atmosphere. All samples showed three mass-loss steps due to the elimination of humidity, decomposition of the non-cellulosic and cellulosic components (main degradation stage of the samples) and thermo-oxidative decomposition of the formed degradation products. The T_onset values corresponding to the main decomposition step, the mass-loss values (%Δm) and the % residual mass (at 600 °C) were influenced by the complexing agent nature as well as the concentration and the action time of the commercial enzyme product. In addition, the calcium content of some samples treated with and without ultrasound was determined using atomic absorption spectroscopy method (AAS) in order to correlate the results with TG/DTG/DTA analysis. The obtained results have shown that the synergistic action of experimental conditions (enzyme concentration, pH, enzyme product action time, ultrasound) and the presence of sodium citrate as a biodegradable complexing agent led to the elimination of a higher amount of pectin from the cotton samples than that eliminated when using EDTA.     

Preparation of cyclophanes by room-temperature ring-closing alkyne metathesis with imidazolin-2-iminato tungsten alkylidyne complexes

Room-temperature ring-closing alkyne metathesis of 1,2-, 1,3-, and 1,4-bis(3-pentynyloxymethyl)benzenes has been investigated in the presence of catalytic amounts of an imidazolin-2-iminato tungsten alkylidyne complex. The m- and p-diynes selectively form the respective [10]metacyclophane or [10.10]paracyclophane, respectively, whereas a mixture of monomeric and dimeric cycloalkynes is obtained in the case of the o-diyne. DFT calculations reveal that the different selectivities can be attributed to the relative thermodynamic stability of the emerging cyclophanes.     

Crystal and Molecular Structure of [2,6‐(Me2NCH2)2C6H3]2SnF2, an Intramolecularly Coordinated Diorganotin Difluoride

Single‐crystal X‐ray diffraction analysis of [2,6‐(Me₂NCH₂)₂C₆H₃]₂SnF₂ reveals that only one of the two dimethylaminomethyl groups of each pincer‐type ligands [2,6‐(CH₂NMe₂)₂C₆H₃]^? is coordinated to the tin atom at Sn‐N distances of 2.576(2) and 2.470(2) Å, inducing chirality of the latter. The tin atom exhibits a distorted octahedral trans(C,C)cis(N,N)cis(F,F) configuration. Extensive intra‐ and intermolecular C‐H···F hydrogen bonding is observed with the latter giving rise to formation of polymeric chains.     

Trace determination of beta-lactam antibiotics in environmental aqueous samples using off-line and on-line preconcentration in capillary electrophoresis

A sensitive and reliable method using capillary zone electrophoresis with UV-diode array detection (CZE-DAD) has been developed and validated for trace determination of beta-lactam antibiotics in waste, well and river water matrices. Due to the lack of sensitivity of the UV-vis detection, a solvent extraction/solid-phase extraction (SPE) method applied for off-line preconcentration and cleanup of water samples, in combination with an on-line preconcentration methodology named large volume sample stacking (LVSS) have been applied. The analytes included nafcillin, dicloxacillin, cloxacillin, oxacillin, ampicillin, penicillin G and amoxicillin. Average recoveries for water samples fortified with the studied beta-lactams at different concentration levels (1.0, 2.0 and 4.0 microg/L) were ranging between 94 and 99%, with relative standard deviations (RSDs) lower than 10%. The precision, calculated as intra-day and inter-day standard deviations fell within acceptable ranges (3.3-7.2%). The limits of detection were estimated to range between 0.08 and 0.80 microgL(-1) for the studied compounds. All the samples analyzed were negative for all the analytes at these levels of concentration and the method showed its usefulness for the detection of these widely applied beta-lactam antibiotics in different kinds of waters.